CN117776965A - Synthesis method of (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand - Google Patents
Synthesis method of (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand Download PDFInfo
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- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003446 ligand Substances 0.000 title claims abstract description 68
- GDOTUTAQOJUZOF-JWCLOVTGSA-N [(1r,2r)-2-azaniumylcyclohexyl]azanium;(2s,3s)-2,3-dihydroxybutanedioate Chemical compound N[C@@H]1CCCC[C@H]1N.OC(=O)[C@@H](O)[C@H](O)C(O)=O GDOTUTAQOJUZOF-JWCLOVTGSA-N 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 20
- LGMKQEGBDGRYII-UHFFFAOYSA-N C(C)O.C(C)(C)(C)C1=C(C(C=O)=CC(=C1)C(C)(C)C)O Chemical compound C(C)O.C(C)(C)(C)C1=C(C(C=O)=CC(=C1)C(C)(C)C)O LGMKQEGBDGRYII-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 98
- 239000012452 mother liquor Substances 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 description 4
- SSJXIUAHEKJCMH-WDSKDSINSA-N (1s,2s)-cyclohexane-1,2-diamine Chemical compound N[C@H]1CCCC[C@@H]1N SSJXIUAHEKJCMH-WDSKDSINSA-N 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- 229960001270 d- tartaric acid Drugs 0.000 description 4
- -1 ethyl 2, 3-epoxyacrylate Chemical compound 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthetic method of (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand, which comprises the following steps: step 1: adding (R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate into a Salen ligand synthesis kettle; step 2: adding deionized water into a Salen ligand synthesis kettle, stirring and dissolving; step 3: dropwise adding 3, 5-di-tert-butyl salicylaldehyde ethanol solution into a Salen ligand synthesis kettle, and completing the reaction; step 4: and (3) transferring the reaction product of the step (3) to a centrifugal machine for separation to obtain Salen ligand. The method has high yield and mild reaction conditions.
Description
Technical Field
The invention relates to a chemical method, in particular to a Salen ligand synthesis method.
Background
Salen, derived from N, N' -bis (salicylaldehydoethylenediamine), is one of the most important ligands in chiral synthesis in recent years. The nature of their metal complexes as catalysts is increasingly known and known as Salen-metal catalysts. The catalyst has wide application in asymmetric catalysis, and is a multifunctional catalyst capable of catalyzing a plurality of reactions. Salen-metal catalysts are particularly effective in the hydrolytic kinetic resolution of epoxy compounds, and are capable of producing nearly pure photoactive epoxy compounds and diols. The resolution mainly uses Salen-Co catalyst, and the effect is remarkable.
From the industrial application point of view, the split of styrene epoxide, propylene oxide, epichlorohydrin and ethyl 2, 3-epoxyacrylate using single-core catalysts has been successful to a ton level. This shows that the use of Salen catalysts in hydrolysis kinetic resolution has been largely practiced.
There are two main methods for preparing binuclear Salen ligands. The first is a two-step synthesis method, namely, firstly, a diamine compound and a derivative of monosalicylaldehyde react to obtain an intermediate, namely, a single condensate of aldehyde and diamine, and the intermediate is separated and then reacts with the derivative of bissalicylaldehyde to obtain the binuclear Salen ligand. However, the reaction for preparing the intermediate in this method is a kinetically and thermodynamically competitive reaction, and the intermediate is extremely easily converted into a mononuclear catalyst ligand after separation, resulting in a low purity of the obtained intermediate, which adversely affects the further preparation of the binuclear Salen ligand. The second method is to adopt a one-pot method, adjust the feeding sequence to firstly feed monoaldehyde, then feed diamine compound and finally add dialdehyde derivative for reaction. The method avoids the transformation problem possibly occurring in the process of separating the intermediate, and more effectively obtains the binuclear ligand.
Patent document US10280185B2 provides a Salen indium catalyst having the general structure wherein R is a coordination alkoxide comprising at least one coordination atom forming a coordination bond with In. The mononuclear salen indium catalyst is particularly useful for catalyzing the ring-opening polymerization of cyclic ester monomers such as lactide. Patent document CN1314661C provides a synthetic method for preparing chiral or achiral binuclear Salen ligands by using chiral or achiral diamines and derivatives of monosalicylaldehyde and bissalicylaldehyde. The method is a synthesis method which comprises the steps of firstly using the derivative of the salicylaldehyde to react with excessive diamine, and then adding excessive derivative of the salicylaldehyde.
The invention provides a reaction method with high yield and simple steps.
Disclosure of Invention
The invention adopts the following scheme to realize the purposes:
a method for synthesizing a (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand, comprising the steps of:
step 1: adding (R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate into a Salen ligand synthesis kettle;
step 2: adding deionized water into a Salen ligand synthesis kettle, stirring and dissolving;
step 3: dropwise adding 3, 5-di-tert-butyl salicylaldehyde ethanol solution into a Salen ligand synthesis kettle, and completing the reaction;
step 4: and (3) transferring the reaction product of the step (3) to a centrifugal machine for separation to obtain Salen ligand.
Further, in the step 1, the mass ratio of the (R, R) -1, 2-diaminocyclohexane-D-tartrate to the potassium carbonate is 1.8-2.2:1.
Further, in the step 1, the mass ratio of the (R, R) -1, 2-diaminocyclohexane-D-tartrate to the potassium carbonate is 1.9-2.1:1.
Further, in the step 2, the mass ratio of deionized water to potassium carbonate is 5-8:1.
Further, the 3, 5-di-tert-butyl salicylaldehyde ethanol solution added dropwise in the step 3 is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol in a mass ratio of 1.9-2.2:4.
Further, the temperature of the Salen ligand synthesis kettle in the step 3 is controlled to be 60-90 ℃.
Further, the step 3 is completed, and the temperature of the Salen ligand synthesis kettle is controlled to be reduced to 0-5 ℃.
And (3) transferring the ethanol mother liquor obtained by separation in the step (4) into an ethanol mother liquor recovery kettle, and performing reduced pressure distillation at the temperature of 30-50 ℃ to obtain ethanol.
Further, the ethanol was distilled under reduced pressure until 90-95% ethanol was obtained, and the collection of ethanol was stopped.
Further, after the collection of ethanol is stopped, the temperature is raised to 70-90 ℃ until the water is evaporated.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the method improves the yield of Salen ligand; 2. the method has mild reaction and is easy to be applied.
Detailed Description
In order to make the technical problems solved, the technical solutions adopted and the technical effects achieved by the present invention more clear, the technical solutions of the embodiments of the present invention will be described in further detail below, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
According to the reaction method, firstly, (R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate generated in the previous working procedure are added into a Salen ligand synthesis kettle according to the mass ratio of 1.8-2.2:1, then deionized water is added by using a metering pump, the mass ratio of the deionized water to the potassium carbonate is 5-8:1, and the deionized water and the potassium carbonate are stirred until the deionized water and the potassium carbonate are dissolved. After complete dissolution, 3, 5-di-tert-butyl salicylaldehyde ethanol solution is added dropwise; the 3, 5-di-tert-butyl salicylaldehyde ethanol solution is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol in a mass ratio of 1.9-2.2:4. In the dropping process, the Salen ligand synthesis kettle is heated at the same time, stirred and gradually heated to 60-90 ℃. After the reaction is finished, cooling the Salen ligand synthesis kettle to 0-5 ℃; the reaction solution was then transferred to a centrifuge for separation. Obtaining yellow solid obtained by separation, namely Salen ligand; separating mother liquor, feeding the mother liquor into an ethanol mother liquor recovery kettle, evaporating ethanol under the conditions of reduced pressure and temperature of 30-50 ℃, condensing and recovering the ethanol, recycling the ethanol, closing an ethanol recovery valve after recovering more than 90-95%, heating to 70-90 ℃ until the water is evaporated, condensing the distilled water and the like, and then feeding the sewage into a kettle for waste treatment.
The reaction equation of the invention is as follows:
in the invention, (R, R) -1, 2-diaminocyclohexane-D-tartrate reacts with K2CO3 to generate potassium tartrate and (R, R) -1, 2-diaminocyclohexane, and simultaneously 3, 5-di-tert-butylsalicylaldehyde and (R, R) -1, 2-diaminocyclohexane are dehydrated to generate Salen ligand.
In the invention, the preparation method of the (R, R) -1, 2-diaminocyclohexane-D-tartrate is as follows:
d-tartaric acid and deionized water are added into a reaction kettle and stirred. After the D-tartaric acid is completely dissolved, gradually heating the reaction kettle to 80-90 ℃, dropwise adding 1, 2-diaminocyclohexane, and stirring; after the completion of the dropwise addition reaction, acetic acid was further added dropwise and stirring was continued. After the dropwise adding reaction is finished, gradually cooling the reaction kettle to 0-5 ℃, and then transferring the materials into a centrifuge for separation to obtain white solid, namely (R, R) -1, 2-diaminocyclohexane-D-tartrate. The D-tartaric acid added dropwise: deionized water: 1, 2-diaminocyclohexane: the weight ratio of the acetic acid is 1.2-1.4:3.9-4.4:1.9-2.1:50.
Reaction principle: 1, 2-diaminocyclohexane is a cis-trans isomer mixture, which consists of (R, R) -1, 2-diaminocyclohexane and (S, S) -1, 2-diaminocyclohexane, wherein the content of the (S, S) -1, 2-diaminocyclohexane is 50%, D-tartaric acid reacts with (R, R) -1, 2-diaminocyclohexane to generate salt, so as to generate (R, R) -1, 2-diaminocyclohexane-D-tartrate, the (R, R) -1, 2-diaminocyclohexane-D-tartrate is precipitated at low temperature, and acetic acid is added after the dropwise addition reaction is finished, so that the (S, S) -1, 2-diaminocyclohexane can react with the (S, S) -1, 2-diaminocyclohexane to generate salt, so that (S, 2-diaminocyclohexane-acetate with stronger solubility is generated, and the (R, R) -1, 2-diaminocyclohexane-D-tartrate is obtained after cooling and separation, the specific reaction principle is as follows:
example 1
(R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate were added to a Salen ligand synthesis vessel at a mass ratio of 1.8:1, followed by deionized water with a metering pump at a mass ratio of 5:1, and stirred until dissolved. After complete dissolution, 3, 5-di-tert-butyl salicylaldehyde ethanol solution is added dropwise; the 3, 5-di-tert-butyl salicylaldehyde ethanol solution is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol in a mass ratio of 1.9:4. In the dropping process, the Salen ligand synthesis kettle is heated at the same time, stirred and gradually heated to 60-90 ℃. After the reaction is finished, cooling the Salen ligand synthesis kettle to 0 ℃; the reaction solution was then transferred to a centrifuge for separation. Obtaining yellow solid obtained by separation, namely Salen ligand; separating mother liquor, feeding the mother liquor into an ethanol mother liquor recovery kettle, evaporating ethanol under the conditions of reduced pressure and 30 ℃, condensing and recovering the ethanol, recycling the ethanol, closing an ethanol recovery valve after recovering more than 90-95 percent of ethanol, heating to 70 ℃ until the water is evaporated, condensing the distilled water and the like, feeding the water into sewage, and treating waste in the kettle residue. .
Example 2
(R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate were added to a Salen ligand synthesis vessel at a mass ratio of 2.2:1, followed by deionized water with a metering pump at a mass ratio of 8:1, and stirred until dissolved. After complete dissolution, 3, 5-di-tert-butyl salicylaldehyde ethanol solution is added dropwise; the 3, 5-di-tert-butyl salicylaldehyde ethanol solution is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol in a mass ratio of 2.2:4. In the dropping process, the Salen ligand synthesis kettle is heated at the same time, stirred and gradually heated to 90 ℃. After the reaction is finished, cooling the Salen ligand synthesis kettle to 5 ℃; the reaction solution was then transferred to a centrifuge for separation. Obtaining yellow solid obtained by separation, namely Salen ligand; separating mother liquor, feeding the mother liquor into an ethanol mother liquor recovery kettle, evaporating ethanol under the conditions of reduced pressure and 50 ℃, condensing and recovering the ethanol for reuse, recovering more than 90-95% of ethanol, closing an ethanol recovery valve, heating to 90 ℃ until the water is evaporated, condensing the distilled water and the like, and then feeding the sewage into a kettle for waste treatment. .
Example 3
(R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate were added to a Salen ligand synthesis vessel at a mass ratio of 1.95:1, followed by deionized water with a metering pump at a mass ratio of 6:1, and stirred until dissolved. After complete dissolution, 3, 5-di-tert-butyl salicylaldehyde ethanol solution is added dropwise; the 3, 5-di-tert-butyl salicylaldehyde ethanol solution is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol in a mass ratio of 2.1:4. In the dropping process, the Salen ligand synthesis kettle is heated at the same time, stirred and gradually heated to 75 ℃. After the reaction is finished, cooling the Salen ligand synthesis kettle to 5 ℃; the reaction solution was then transferred to a centrifuge for separation. Obtaining yellow solid obtained by separation, namely Salen ligand; separating mother liquor, feeding the mother liquor into an ethanol mother liquor recovery kettle, evaporating ethanol under the conditions of reduced pressure and 40 ℃, condensing and recovering the ethanol for reuse, recovering more than 90-95% of ethanol, closing an ethanol recovery valve, heating to 80 ℃ until the water is evaporated, condensing the distilled water and the like, and then feeding the sewage into a kettle for waste treatment.
Example 4
(R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate were added to a Salen ligand synthesis vessel at a mass ratio of 2.1:1, followed by deionized water with a metering pump at a mass ratio of 7:1, and stirred until dissolved. After complete dissolution, 3, 5-di-tert-butyl salicylaldehyde ethanol solution is added dropwise; the 3, 5-di-tert-butyl salicylaldehyde ethanol solution is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol in a mass ratio of 2.0:4. In the dropping process, the Salen ligand synthesis kettle is heated at the same time, stirred and gradually heated to 80 ℃. After the reaction is finished, cooling the Salen ligand synthesis kettle to 5 ℃; the reaction solution was then transferred to a centrifuge for separation. Obtaining yellow solid obtained by separation, namely Salen ligand; separating mother liquor, feeding the mother liquor into an ethanol mother liquor recovery kettle, evaporating ethanol under the conditions of reduced pressure and 50 ℃, condensing and recovering the ethanol, recycling the ethanol, closing an ethanol recovery valve after recovering more than 90-95%, heating to 80 ℃ until the water is evaporated, condensing the distilled water and the like, and then feeding the sewage into a kettle for waste treatment.
Example 5
(R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate were added to a Salen ligand synthesis vessel at a mass ratio of 2.1:1, followed by deionized water with a metering pump at a mass ratio of 6:1, and stirred until dissolved. After complete dissolution, 3, 5-di-tert-butyl salicylaldehyde ethanol solution is added dropwise; the 3, 5-di-tert-butyl salicylaldehyde ethanol solution is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol in a mass ratio of 2.0:4. In the dropping process, the Salen ligand synthesis kettle is heated at the same time, stirred and gradually heated to 80 ℃. After the reaction is finished, cooling the Salen ligand synthesis kettle to 0 ℃; the reaction solution was then transferred to a centrifuge for separation. Obtaining yellow solid obtained by separation, namely Salen ligand; separating mother liquor, feeding the mother liquor into an ethanol mother liquor recovery kettle, evaporating ethanol under the conditions of reduced pressure and 40 ℃, condensing and recovering the ethanol for reuse, recovering more than 90-95% of ethanol, closing an ethanol recovery valve, heating to 80 ℃ until the water is evaporated, condensing the distilled water and the like, and then feeding the sewage into a kettle for waste treatment.
The Salen ligand in the above example was taken and weighed, and the yields of the comparative Salen ligand were as follows.
| Salen ligand yield | |
| Example 1 | 95.11 |
| Example 2 | 95.24 |
| Example 3 | 96.21 |
| Example 4 | 95.93 |
| Example 5 | 95.45 |
The above yields are based on 3, 5-di-tert-butylsalicylaldehyde to yield Salen ligand.
Compared with the prior art, the method of the invention has the advantages that the finished product is obtained by adding the salicylaldol solution to react with the potassium carbonate, the yield is high, and the reaction condition is mild.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (10)
1. A method for synthesizing a (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand, characterized by comprising the steps of:
step 1: adding (R, R) -1, 2-diaminocyclohexane-D-tartrate and potassium carbonate into a Salen ligand synthesis kettle;
step 2: adding deionized water into a Salen ligand synthesis kettle, stirring and dissolving;
step 3: dropwise adding 3, 5-di-tert-butyl salicylaldehyde ethanol solution into a Salen ligand synthesis kettle, and completing the reaction;
step 4: and (3) transferring the reaction product of the step (3) to a centrifugal machine for separation to obtain Salen ligand.
2. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 1, wherein:
in the step 1, the mass ratio of the (R, R) -1, 2-diaminocyclohexane-D-tartrate to the potassium carbonate is 1.8-2.2:1.
3. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 2, wherein:
in the step 1, the mass ratio of the (R, R) -1, 2-diaminocyclohexane-D-tartrate to the potassium carbonate is 1.9-2.1:1.
4. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 1, wherein:
in the step 2, the mass ratio of deionized water to potassium carbonate is 5-8:1.
5. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 1, wherein:
the 3, 5-di-tert-butyl salicylaldehyde ethanol solution added dropwise in the step 3 is prepared from 3, 5-di-tert-butyl salicylaldehyde and absolute ethanol with the mass ratio of 1.9-2.2:4.
6. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 1, wherein:
the temperature of the Salen ligand synthesis kettle in the step 3 is controlled to be 60-90 ℃.
7. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 1, wherein:
and 3, completing the reaction, and controlling the temperature of the Salen ligand synthesis kettle to be reduced to 0-5 ℃.
8. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 1, wherein:
transferring the ethanol mother liquor obtained by separation of the centrifuge in the step 4 into an ethanol mother liquor recovery kettle, and heating at the temperature
And distilling under reduced pressure at 30-50 ℃ to obtain ethanol.
9. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 7, wherein:
the ethanol was distilled under reduced pressure until 90-95% ethanol was obtained, and the collection of ethanol was stopped.
10. The method for synthesizing (R, R) -1, 2-diaminocyclohexane-D-tartrate Salen ligand according to claim 8, wherein:
after stopping collecting ethanol, heating to 70-90deg.C until water is evaporated.
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